The structures of the water-insoluble complexes of acrylate-based copolymers containing diazosulfonate groups and a fluorinated cationic surfactant (Hoe L-3658-1) were examined by X-ray diffraction, contact angle measurements, differential scanning calorimetry, and spectroscopic methods (IR, UV-vis, fluorescence). The structures of the complexes were shown to be lamellar and determined by using Ruland's interface distribution function procedure. Remarkably low critical surface tensions were found. indicating the formation of ordered layers of fluorocarbon segments at the surfaces of the complexes. Fine-tuning of the complex structures was achieved by varying the composition of the copolymers as well as the pH value present at the time of preparation. The formation of excimers was found to be strongly influenced by the complex structure.